1310780 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種應用熱可塑性聚醯亞胺之雙面基層 板及其製法，尤其係指一種可減少基板厚度，並具有尺寸 安定性、耐藥性、耐熱性、耐曲折性及製程簡單特點之雙 面基層板及其製法。 【先前技術】 目前軟性電路板在製造上，已多用聚醯亞胺（P I ) 來製作其基層板’而由於電子產品之小型化、輕量化及性 能化要求，此種對於輕量、小型具有極大貢獻之電路軟板 亦同樣的被廣泛的應用在目前如手機、筆記型電腦亦或個 人行動式資訊處理器（PDA)上。 —般應用聚醯亞胺之基層板在製造時，多係先在一個 廠k佈和乾栋聚醯胺酸形成聚醯亞胺薄膜，再將此膜 ^ ^ __ ' —個工廠中進行塗佈接著劑並與銅箔壓合後形成單 面銅：基層板’另-方面，於此單面銅箔基層版之產物塗 布接著劑並與銅箱壓合後形成雙面面銅辖基層★，以供後 續線路加工之用。 兩個不同的工廠進行 ’因此製作成木上+公的又效么τ<破&1310780 IX. Description of the Invention: [Technical Field] The present invention relates to a double-sided base plate using a thermoplastic polyimide, and a method for producing the same, and particularly to a substrate thickness reduction, dimensional stability, and resistance Double-sided base plate with medicinal properties, heat resistance, tortuosity resistance and simple process characteristics, and a method for preparing the same. [Prior Art] At present, flexible circuit boards have been manufactured using polyimine (PI) to make their base sheets. Due to the miniaturization, weight reduction and performance requirements of electronic products, this is lightweight and compact. The circuit board that has contributed greatly is also widely used in mobile phones, notebook computers or personal mobile information processors (PDAs). In general, the base plate of polyimine is used to form a polyimide film in a factory k-cloth and dry poly-polyamine, and then the film is coated in a factory. The adhesive is bonded to the copper foil to form a single-sided copper: the base layer plate is another side. The product of the single-sided copper foil base layer is coated with an adhesive and pressed into a copper box to form a double-sided copper base layer. For subsequent processing of the line. Two different factories carry out 'so make a wooden + public effect τ < broken &
的優異， ·—述製作聚醯亞胺基層板之方式，由於必須要在 應用特別明顯，又，由於環氧樹脂 異’因此容易發生聚醯亞胺/銅箔 1310780 介面剝離，影響基層板的可靠性。 、又，傳統的雙面銅箔聚醯亞胺基層板在厚度上，通常 :乍為基，的聚醯亞胺層厚度為2 5…於基板之雙面所 塗佈之環氧樹脂接著劑層厚度為工2私m，再加上設置在 =者劑層上之銅箔層厚度為丄8 # m ’使得雙面聚醯亞胺 :層板之整體厚度高達8 5 ’因此如可降低此一整體 厚度’簡化製程並提高其安定性及耐化性 φ，使用範圍、市場接受率及應用度大幅的提升：= 提尚產品的競爭力。 【發明内容】 本&月人有鑒於上述需求，乃積極著手進行研發，以 期可以達到預期之效果，經過不斷的試驗及努力，終於研 發出本發明。 本發明之主要目的在於提供一種應用熱可塑性聚醯亞 胺之雙面基層板及其製法。 • 為了達到上述發明目的，本發明之應用熱可塑性聚醯 亞胺之雙面基層板製法係包含下述步驟： 聚酿胺酸（ΡΑΑ)製作，係以芳香族二胺及芳香族 ®叛酸二gf溶於極性非質子溶劑中反應生成聚酿胺酸； 熱可塑性聚醯亞胺（tp I )製作，係以芳香族二胺 及芳香族四羧酸二酐溶於極性非質子溶劑中反應生成聚醯 胺S文，再經由共沸劑尚溫環化以製成熱可塑性聚醯亞胺； 基層板製作步驟，係以共擠壓之方式一次將熱可塑性 聚醢亞胺、聚醯胺酸及熱可塑性聚醯亞胺之三層結構塗佈 6 1310780 在一銅箔上； 壓合步驟’係將基層板製作步驟之產物外層熱可塑性 聚醯亞胺上設置另一銅猪板於高溫高壓下壓合成為成品。 上述壓合步驟之壓合溫度在2 〇 〇。卜4 〇 W，壓 合壓力在 5Kg/cm2〜2〇〇Kg/cm2。 上述熱可塑性聚醯亞胺（丁P I)製作中所使用之芳 香族四羧酸二酐係選自於苯均四羧酸二酐、3,3, ，4, 4，-二苯基四羧酸二酐、3,3，，4,4，—二苯甲輞 四羧酸二酐、4,4,一氧二苯二酸二酐、3,3, ，4,4， -二苯基剌吨酸二肝、2,2 —雙（3,4_^缓基笨 基）六氟丙烷、乙二醇一雙偏苯三酸酐；該芳香族二胺係 選自對3’4，-二胺基二苯基醚、4,4’ —二胺基二笨 基醚、對苯二胺、2,4 一甲苯二胺、3, 5_二胺基笨甲 酸、2, 2 —雙（4 —胺基苯基）丙烷、4, 4，一二胺基 二苯基甲烷、4, 4，一二胺基二苯基磺醯、3,3，—二 胺基二苯基磺醯、4，4，一二胺基二苯基硫、1，3 — 雙（4 一胺基笨氧基）苯、1，3 一雙一胺基苯氧基） 苯、1,4 —雙（4 —胺基苯氧基）苯、4,4 一雙（4一 胺基苯氧基）~聯苯、2, 2 —雙一4 — (4 —胺基笨氧 基）苯、2,2 —雙一4 — (3~胺基笨氧基）苯、2,2 一一曱基一4，4 —二胺基聯苯、3，3 —二甲基~4，4 一 fe基聯苯、3,3 —二烴基一 4, 4 —二胺基聯苯。 其中’上述之芳香族二胺與芳香族四羧酸二酐間之相 對重量比為0.8〜1.2。 7 1310780 本發明之熱可塑性聚醯亞胺之雙面基層板係包括有聚 醯胺酸所形成之聚醯亞胺層’於該層之兩面設有作為接著 劑之熱可塑性聚醢亞胺層，在各熱可塑性聚醯亞胺層之上 設置有銅箔板。 上述聚醯亞胺基板之厚度為1 2 〜2 5 /zm ;熱 可塑性聚醯亞胺層之厚度為1 Mm〜1 。 【實施方式】 丰發明應用熱可塑性聚醯亞胺之雙面基層板製法係包 含下述步驟： 聚醯胺酸（p A A )製作，係以芳香族二胺及芳香族 四羧酸二酐溶於極性非質子溶劑中反應生成聚醯胺酸； 熱可塑性聚醯亞胺（T P j )製作，係以芳香族二胺 及芳香族四羧酸二酐溶於極性非質子溶劑中反應生成聚醯 胺酸，再經由共沸劑高溫環化以製成熱可塑性聚醯亞胺； 基層板製作步驟，係以共擠壓之方式一次將熱可塑性 聚醯亞胺、聚醯胺酸及熱可塑性聚醯亞胺之三層結構塗佈 在一銅箔上； 壓合步驟，係將基層板製作步驟之產物外層熱可塑性 聚醯亞胺上設置另一銅箔板於高溫高壓下壓合成為成品。 現就牟發明之具體實施例進行說明。 聚酿胺酸（PAA)製作，省土制τ ji. _ 衣作’百先製備PI前驅液之聚 醢胺酸，係取笨二胺1支、」 ,, X β 胶兄 4,4 —二胺基二苯基醚2 克和二甲基呋喃35克攪拌溶解，加入33， 4,4， -二苯基四羧酸二酐5.9奋婭0/1 , η* , y兄、& 2 4小時反應生成黏度約 8 1310780 為50000cps之聚醢胺酸’此該聚醯胺酸製作乃 是一般具有丰案通常知識之人士所熟知之習知技術，因此 其過程便省略說明。 熱可塑性聚醯亞胺（TP I )製作，係取5.8克之 1，4_雙（4 —胺基苯氧基）苯與56克1)]^1?攪拌溶 解，加入8. 2克之乙二醇一雙偏苯三酸酐反應生成聚醯 胺酸’再加入甲苯（共沸劑）升溫至2 ◦ 反應2 4小 時，經環化脫水後形成黏度約為2 〇 〇 〇 〇 c p s之熱可 塑性聚醢亞胺。 基層板製作步驟，係以共擠壓之方式一次將熱可塑性 聚醯亞胺、聚醯胺酸及熱可塑性聚醯亞胺之三層結構塗佈 在一銅箔上，在2 〇 〇 t之溫度下去除大部分之溶劑，再 經4 0 0 C之高溫使之環化完全。Excellent, · The method of making polyimine-based laminates, because it must be particularly obvious in the application, and because of the epoxy resin, it is easy to occur the interfacial peeling of the polyimide/copper foil 1310780, affecting the substrate reliability. Moreover, the conventional double-sided copper foil polyimide substrate layer has a thickness of usually 乍, and the polyimide layer has a thickness of 25 Å... an epoxy resin adhesive coated on both sides of the substrate The thickness of the layer is 2 m, and the thickness of the copper foil layer set on the layer of the agent is 丄8 # m ', so that the double-sided polyimine: the overall thickness of the laminate is as high as 8 5 ' This overall thickness 'simplifies the process and improves its stability and chemical resistance φ. The scope of use, market acceptance and application are greatly improved: = The competitiveness of the product is improved. SUMMARY OF THE INVENTION This & month person has actively pursued research and development in view of the above-mentioned needs, in order to achieve the desired effect, and has finally developed the present invention through continuous experimentation and efforts. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a double-sided base sheet using a thermoplastic polyimide, and a process for producing the same. In order to achieve the above object, the double-sided base plate method for applying thermoplastic polyimine of the present invention comprises the following steps: Preparation of polyacrylic acid (anthracene) with aromatic diamine and aromatic acid The di-gf is dissolved in a polar aprotic solvent to form poly-aracine; the thermoplastic polyimine (tp I ) is prepared by dissolving aromatic diamine and aromatic tetracarboxylic dianhydride in a polar aprotic solvent. Producing a polyamidamine S, and then cyclizing at a temperature by an azeotropic agent to form a thermoplastic polyimine; a base layer forming step of co-extruding the thermoplastic polyimine, polyamine The three-layer structure of acid and thermoplastic polyimine is coated on 6 1310780 on a copper foil; the pressing step is to set another copper pig plate on the outer layer of the thermoplastic layer of the product of the base layer preparation step at a high temperature. Pressed under high pressure to form a finished product. The pressing temperature of the above pressing step is 2 〇 〇. Bu 4 〇 W, the pressing pressure is 5Kg/cm2~2〇〇Kg/cm2. The aromatic tetracarboxylic dianhydride used in the preparation of the above thermoplastic polyimine (butyl PI) is selected from the group consisting of pyromellitic dianhydride, 3,3,4,4,-diphenyltetracarboxylic acid. Acid dianhydride, 3,3,,4,4,dibenzoguanidine tetracarboxylic dianhydride, 4,4,monooxydiphthalic dianhydride, 3,3,4,4,-diphenyl剌tanoic acid di-hepatic, 2,2-bis(3,4-^ succinyl) hexafluoropropane, ethylene glycol mono-trimellitic anhydride; the aromatic diamine is selected from the group consisting of 3'4,-diaminodi Phenyl ether, 4,4'-diaminodiphenyl ether, p-phenylenediamine, 2,4-toluenediamine, 3,5-diaminobenzoic acid, 2,2-bis(4-amino Phenyl)propane, 4,4,monodiaminodiphenylmethane, 4,4,monodiaminodiphenylsulfonium, 3,3,diaminodiphenylsulfonium, 4,4, Monodiaminodiphenylsulfide, 1,3-bis(4-aminophenyloxy)benzene, 1,3-bis-aminophenoxy)benzene, 1,4-bis(4-aminobenzene) Oxy)benzene, 4,4-bis(4-aminophenoxy)~biphenyl, 2,2-di- 4-(4-aminophenyloxy)benzene, 2,2-double-4 (3~Amino-p-oxy)benzene, 2,2 A fluorenyl-4,4-diaminobiphenyl, 3,3-dimethyl-4,4-mono-biphenyl, 3,3-dihydrocarbyl-4,4-diaminobiphenyl. Wherein the relative weight ratio between the above aromatic diamine and the aromatic tetracarboxylic dianhydride is from 0.8 to 1.2. 7 1310780 The double-sided base plate of the thermoplastic polyimine of the present invention comprises a polyimine layer formed of poly-proline to provide a thermoplastic polyimine layer as an adhesive on both sides of the layer. A copper foil plate is disposed on each of the thermoplastic polyimide layers. The polyimide substrate has a thickness of 1 2 to 2 5 /zm; and the thermoplastic polyimide layer has a thickness of 1 Mm 1 . [Embodiment] The double-sided base plate manufacturing method using the thermoplastic polyimide polyimide comprises the following steps: Polylysine (p AA ) is prepared by dissolving aromatic diamine and aromatic tetracarboxylic dianhydride. The reaction is carried out in a polar aprotic solvent to form poly-proline; the thermoplastic polyimine (TP j ) is prepared by dissolving aromatic diamine and aromatic tetracarboxylic dianhydride in a polar aprotic solvent to form polyfluorene. The amine acid is further cyclized at a high temperature by an azeotropic agent to form a thermoplastic polyimine; the base layer is prepared by co-extruding the thermoplastic polyimine, polylysine and thermoplastic at one time. The three-layer structure of quinone imine is coated on a copper foil; the pressing step is to press another copper foil plate on the outer layer of the thermoplastic polyimide polyimide to form a finished product under high temperature and high pressure. A specific embodiment of the invention will now be described. Made from polyaminic acid (PAA), the soil-saving system τ ji. _ 衣衣 'Bai Xian preparation of PI prodrug poly-proline, is a stupid diamine,", X β plastic brother 4,4 — 2 g of diaminodiphenyl ether and 35 g of dimethylfuran were stirred and dissolved, and 33, 4,4,-diphenyltetracarboxylic dianhydride 5.9 Fenya 0/1, η*, y brother, & The reaction of 24 hours produces a polyamic acid having a viscosity of about 8 1310780 of 50,000 cps. The production of the polyamic acid is a well-known technique well known to those who generally have a general knowledge of the case, and the description thereof is omitted.克乙乙二。 The thermoplastic polyimine (TP I), 5.8 grams of 1,4 bis (4-aminophenoxy) benzene and 56 grams of 1)] ^ 1? The alcohol-ditrimellitic anhydride is reacted to form poly-proline acid, and then toluene (azeotropic agent) is added to raise the temperature to 2 ◦ for 24 hours, and after dehydration by cyclization, a thermoplastic polyimine having a viscosity of about 2 〇〇〇〇cps is formed. . The base layer manufacturing step is to apply a three-layer structure of thermoplastic polyimine, poly-proline and thermoplastic polyimine on a copper foil in a co-extrusion manner at 2 〇〇t Most of the solvent is removed at temperature and then cyclized completely at a temperature of 400 °C.
壓合步驟，係將基層板製作步驟之產物外層熱可塑性聚 醯亞胺上設置另-鋼箔板於3 8 0。。之溫度、100Kg /cm2之壓力下壓合5分鐘成為成品。 上述之應用熱可塑性聚醯亞胺之雙面基層板依據〗p 5〇 2· 4 . 9方法測試其熱可塑性聚醯亞胺 與銅猪板之剝離強度，其測試値為1.2 1 kg "cm。 依據 IPC 〜丁 Λ Α _ 丄Μ 6 5 0 2. 4 . 4 C方法測視其尺 寸安定性’其測試値為0 · 〇 8 %。 由上述方去所製造之丰發明應用熱可塑性聚醯亞胺 之雙面基層板中，你 作為基板的聚隨亞胺層厚度為17 Π1 ’於基板之勢而& 、 又面所塗佈之熱可塑性聚醯亞胺接著劑層厚 9 1310780 度為4…再加上設置在接著劑層上之銅箱層厚度為工 8 ，使彳于雙面聚醯亞胺基層板之整體厚度僅有6 1 # m，故可以降低雙面基層板之整體厚度，X，因為牟發^ 係利用壓合法製成，因此製程簡單、良率高，且由於作為 接著劑之熱可塑性聚醯亞胺與作為基板之聚酿亞胺均屬於 聚醯亞胺士列，因此能夠以極低之厚度需求來達成銅箱板 之穩固接著效果，此係由於熱可塑性聚醯亞胺在3 〇 〇 =上之溫度時’可藉由壓力配合產生融熔現象使得其與銅 箔板表面產生良好的接著效果之故。 經由上述說明，丰發明至少具有以下之優點： 1熱可塑性聚醯亞胺耐熱性比傳統接著劑佳，因此 可以增加基層板之尺寸安定性； 2、熱可塑性聚醯亞胺耐藥性比傳統接著劑佳，因此 可以防止聚醯亞胺/銅箔介面剝離’ $而影響到基層板的 可靠性； 3熱可塑性聚醯亞胺比傳統接著劑之絕緣電阻大， 因此可以防止離子遷移所造成之訊號短路現象； 4由於係屬無膠雙面銅箔基層板，因此在製程時間 上可縮減一半以上而具有市場競爭力、 5、可降低基層板整體厚度，符合現今電子產品強調 輕薄短小之市場需求。 以下即為本案之產品與既有兩層式雙面基板作一比較 之比較表。 1310780 項 巨 單位 兩層式雙面板 三層式雙面板 收縮率 蝕刻後 TD % 0.012 0.114 MD -0.005 -0.019 表面絕緣阻抗 C-96/20/65 — Ω 2.2139X1016 3.73xl014 收縮率大小表蝕刻後線路的尺寸安定性 由上表可知，本案之三層雙面基板較以往之兩層雙面 基板具有更加之尺寸安定性。 【圖式簡單說明】In the pressing step, the outer layer of the thermoplastic layer of the product of the base layer forming step is provided with a steel foil plate at 380. . The temperature was pressed at a pressure of 100 kg/cm 2 for 5 minutes to become a finished product. The double-sided baseboard of the above-mentioned thermoplastic polyimine was tested for peel strength of the thermoplastic polyimine and the copper pig board according to the method of 〇p 5〇2·4.9, and the test enthalpy was 1.2 1 kg " Cm. According to IPC ~ Ding Λ _ _ 丄Μ 6 5 0 2. 4 . 4 C method to measure its dimensional stability 'the test 値 is 0 · 〇 8 %. In the double-sided base sheet of the thermoplastic polymerized polyimide which is manufactured by the above-mentioned method, the thickness of the polyimine layer as a substrate is 17 Π1 ' on the surface of the substrate and coated on the surface. The thermoplastic polyimine adhesive layer thickness is 9 1310780 degrees 4...plus the thickness of the copper box layer disposed on the adhesive layer is 8 , so that the overall thickness of the double-sided polyimide layer is only There is 6 1 # m, so the overall thickness of the double-sided base plate can be reduced, X, because the hair is made by pressing, so the process is simple, the yield is high, and the thermoplastic polyimide is used as an adhesive. Both the polyimine and the substrate are polyamidiamines, so the stable adhesion effect of the copper box can be achieved with extremely low thickness requirements due to the thermoplastic polyimine at 3 〇〇 = At the temperature, the melt can be caused by a press fit to produce a good adhesion effect with the surface of the copper foil. Through the above description, the invention has at least the following advantages: 1. The thermoplastic polyimine has better heat resistance than the conventional adhesive, so that the dimensional stability of the base plate can be increased; 2. The thermoplasticity of the polyimide is more resistant than the conventional one. The agent is good, so it can prevent the polyimide/copper foil interface from peeling off, which affects the reliability of the substrate. 3 The thermoplastic polyimide has higher insulation resistance than the conventional adhesive, thus preventing ion migration. Short-circuit phenomenon of signal; 4Because it is a double-sided copper foil base board without glue, it can be reduced in process time by more than half and has market competitiveness. 5. It can reduce the overall thickness of the base board, which is in line with the current emphasis on light and thin electronic products. Market demand. The following is a comparison table between the product of this case and the existing two-layer double-sided substrate. 1310780 item giant unit two-layer double-panel three-layer double-panel shrinkage after etching TD % 0.012 0.114 MD -0.005 -0.019 Surface insulation resistance C-96/20/65 — Ω 2.2139X1016 3.73xl014 Shrinkage size table after etching Dimensional stability As can be seen from the above table, the three-layer double-sided substrate of the present invention has more dimensional stability than the conventional two-layer double-sided substrate. [Simple description of the map]
【主要元件符號說明】[Main component symbol description]